CN105330867B - A kind of organic fluorinated silicone surface conditioning agent and preparation method thereof - Google Patents
A kind of organic fluorinated silicone surface conditioning agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of organic fluorinated silicone surface conditioning agent and preparation method thereof；A kind of organic silicon-fluorine surface conditioning agent of the present invention, for the reactant based on amino silicane coupling agent, amino silicones and epoxy based polysiloxane, using hexafluoropropylene trimer as modifying agent, using glycol dimethyl ether as solvent, using triethylamine as catalyst, by react synthesis fluosilicic oxyalkane compound or on side chain introduce perfluoroalkyl fluorosiloxane copolymer.The present invention is without by connecting Mr. chain structure into reaction intermediate, synthetic route is succinct, and high conversion rate, the organic fluorinated silicone compound of preparation has high surface and high stability, it can be used to the waterproof of fabric, grease proofing and soil resistant finish, it may also be used for metal, the waterproof and antifouling process of construction material.
Description
Technical field
The present invention relates to a kind of organic fluorinated silicone compound, more particularly to a kind of organic fluorinated silicone surface conditioning agent and its preparation side
Method.
Background technology
Fluoride silicon surfactant is widely used in material guarantor due to its distinctive low surface tension and chemical resistance properties
The multiple fields such as shield, building coating, textile, industry cleaning link, fire-fighting fire extinguishing and agricultural chemicals.As fluorosilicone reaction product can be used as
The surface conditioning agent of the materials such as textile, assign material excellent water repellency, oil repellent, resistance to soiling and sense of touch.In order to such as spinning
The matrix such as fabric provide water, oil and soil repellent and flexibility simultaneously, a kind of to include the perfluoroalkyl provided and offer flexibility
The water and oil repellant composition of silicone compounds has been used widely.Current organic fluorinated silicone surfactant both at home and abroad
Synthesis is mainly in following direction：1st, hydrosilation method：By Fluorine containing olefine or fluoroalkyl alkene ether and silane containing hydrogen or contain
The hydrosilylation synthesis of hydrogen silicone oil；2nd, radical polymerization：Pass through Fluorine containing olefine or fluoroalkyl alkene ether and silicon containing double bond
The free copolyreaction synthesis of alkane；3rd, functional group reactionses method：Such as quaterisation and epoxide group ring-opening reaction.
Japan Patent JP-A-02-214791 and JP-A-03-231986 are disclosed using fluorinated acrylate monomer and silicon
The method that oxygen alkane acrylate monomer synthesizes fluorosilicone by copolyreaction.Because perfluoroalkyl acrylate esters polymer has high dredge
It is water-based, thus in emulsion polymerization, the very big necessity of the amount of used emulsifying agent be present, the type of emulsifying agent is restricted
The problem of and due to very poor with another fluorine-free monomer compatibility and should use cosolvent necessity；In polymerisation in solution,
The problem of caused dissolubility in polymer solvent of by the same token reduces be present.
The A of Chinese patent CN 103554480 disclose a kind of preparation method of fluorosilicone：With the first of the base containing perfluorinated nonene
Base acrylate is raw material, and hydrosilylation occurs with dimethyl dichlorosilane (DMCS) under chloroplatinic acid-catalysis, obtains among fluorine silicon
Body 2- methyl -2- perfluorinated nonene epoxide ethoxycarbonylethyl group dimethyl dichlorosilane (DMCS)s, continue to react with PEG-4000, synthesis
2- methyl -2- perfluorinated nonene epoxide ethoxycarbonylethyl group methyl dimerization Ethoxysilanes.The catalyst that this method uses
It is inefficient, it is impossible to obtain very high yield, and generated with substantial amounts of accessory substance；Need to synthesize fluorine silicon intermediate simultaneously,
Synthetic method route is long, technical requirements are complicated, therefore production cost is higher.
Hexafluoropropylene trimer, wide material sources, relative low price, its derivative can be used as surfactant.Hexafluoro third
Alkene tripolymer can obtain corresponding anionic fluorosurfactants, and fluorine-containing latex with aromatics sulfonic acid, carboxylic acid reaction
Surfactant of polymerization etc..Fluorine-containing surfactant is synthesized by fluorine-containing precursor material of hexafluoropropylene trimer, two sides be present
The subject matter in face：First, the perfluoroalkyl chain of hexafluoropropylene trimer is short compared with PFOS and PFOA, and has collateralization structure,
Therefore the surface-active of hexafluoropropylene trimer derivative is relatively poor, is not yet used widely；Second, hexafluoropropene trimerization
Body performs the derivatization as fluorine-containing precursor material, and reaction type is mainly the nucleophilic displacement of fluorine of vinyl fluoride, typically passes through alkyl parent
Compound stability difference derived from core reagent is, it is necessary to select the stable connection chain structure of chemical property to improve its stability.Such as
Chinese patent CN 103554480A use the methacrylate of the base containing perfluorinated nonene to pass through methacrylic acid ester group for raw material
Connection chain structure so that derivative synthesis fluoride silicon surfactant；If Chinese patent CN 103432959B are with hexafluoropropene trimerization
Body is fluorine-containing precursor material, using phenyl ring as the chain that is rigidly connected, is prepared using hexafluoropropylene trimer as the fluorine-containing of hydrophobic units
Surfactant.The introducing of connects chain so that synthetic route complicates, while conversion ratio reduces, production cost rises, and then limits
Widely using for hexafluoropropylene trimer class surfactant is made.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of organic fluorinated silicone surface conditioning agent and its preparation
Method；The present invention is without by connecting Mr. chain structure into reaction intermediate, synthetic route is succinct, and high conversion rate, prepares
Organic fluorinated silicone compound there is high surface and high stability, you can it is grease proofing and antifouling whole for the waterproof of fabric
Reason, it may also be used for metal, the waterproof and antifouling process of construction material.
To achieve these goals, a kind of organic silicon-fluorine surface conditioning agent of the invention, it is with amino silicane coupling agent, ammonia
Reactant based on based polysiloxane or epoxy based polysiloxane, using hexafluoropropylene trimer as modifying agent, with glycol dinitrate
Ether is solvent, using triethylamine as catalyst, by reacting the fluosilicic oxyalkane compound of synthesis or perfluoroalkyl being introduced on side chain
Fluorosiloxane copolymer.
Preferably, shown in the structure of the hexafluoropropylene trimer such as formula (I)：
(I)：
As further preferred, the hexafluoropropylene trimer is perfluor -4- methyl -3- isopropyls amylene -2.
Preferably, the amino silicones are side-chain amino group silicone oil or block polyether amino silicone oil.
Preferably, shown in the general structure of the amino silicane coupling agent such as formula (II)：
(Ⅱ)：Y-(CH2)n-Si-R3
In formula：Y is nitrogenous class group
N=2-3
R is alkyl or hydrolyzable alkoxy.
As further preferred, the structural formula of the amino silicane coupling agent is NH2CH2CH2CH2Si(OC2H5)3Or
NH2CH2CH2NHCH2CH2CH2SiCH3(OCH3)2。
As further preferred, the general structure of the side-chain amino group silicone oil is：
In formula：X=NHC2H4NH2、NHC3H6N(CH3)2、N(C2H4NH2)2
R=OH or CH3。
As still more preferably, the general structure such as formula (III) of the side-chain amino group silicone oil is shown：
(Ⅲ)：
As further preferred, shown in the general structure such as formula (IV) of the block polyether amino silicone oil：
(Ⅳ)：
Wherein：X=1-10；Y=1-10；Z=1-10.
Preferably, shown in the general structure such as formula (V) of the epoxy based polysiloxane：
(Ⅴ)：
The present invention passes through NH2 the or NH groups and hexafluoropropylene trimer in amino silicane coupling agent, amino silicones
Double bond fluorine atom nucleophilic substitution occurs, the double bond of epoxide group and hexafluoropropylene trimer on epoxy based polysiloxane
The compound or polymer that fluorine atom generation ring-opening reaction is prepared can be used as organic fluorinated silicone surface conditioning agent.The present invention's has
Machine fluorine silicon face inorganic agent combines the double properties of organosilicon and fluorocarbons, has both maintained intrinsic excellent resistance to of silicone oil
High temperature performance, viscosity temperature characteristic, and can make the waterproof of fluorosilicon oil, and oil resistant solvent resistance improves, and assigns material special performance.
It is a further object of the present invention to provide a kind of preparation method of organic silicon-fluorine surface conditioning agent, including fluorosilicone
The preparation method of compound and fluorosiloxane copolymer；
The preparation method of wherein fluosilicic oxyalkane compound comprises the following steps：Glycol dinitrate is sequentially added into reaction bulb
Ether, triethylamine, hexafluoropropylene trimer, stir, and amino silicane coupling agent is added dropwise after being warming up to 40-50 DEG C, and control is added dropwise
Time is 30-50min, after being added dropwise under the conditions of 40-60 DEG C, reacts 3h；Reaction terminates, under the conditions of 0.1Mpa, 90 DEG C
It is evaporated under reduced pressure and removes solvent glycol dimethyl ether, catalyst of triethylamine and unreacted hexafluoropropylene trimer；Pass through backflow or molten
Parse method and remove unreacted amino silicane coupling agent and accessory substance triethylamine hydrofluoride, crude product is purified；
The preparation method of wherein fluorosiloxane copolymer comprises the following steps：Glycol dinitrate is sequentially added into reaction bulb
Ether, triethylamine, amino silicones or epoxy based polysiloxane, lead to nitrogen protection stirring, hexafluoropropene trimerization is added dropwise at room temperature
Body, it is 30-50min to control time for adding, and glycol dimethyl ether is added after being added dropwise and maintains room temperature 30min, is then heated to
40-80 DEG C, react 3h；Reaction terminates, and is evaporated under reduced pressure under the conditions of 0.1MPa, 70 DEG C and removes low-boiling point material.
Preferably, in the preparation method of fluosilicic oxyalkane compound, the amino silicane coupling agent is the second of aminopropyl three
TMOS, the method that the backflow removes unreacted amino silicane coupling agent and accessory substance triethylamine hydrofluoride are：
Running water is added after vacuum distillation in reaction bulb, heating is stirred at reflux 60min, is cooled to room temperature, filters, and drying obtains target
Product, then plus glycol dimethyl ether, flow back further purification, filtering drying obtain khaki powder shape solid.
Preferably, in the preparation method of fluosilicic oxyalkane compound, the amino silicane coupling agent is aminoethyl ammonia third
Ylmethyl dimethoxysilane, the solution modeling remove unreacted amino silicane coupling agent and accessory substance triethylamine hydrogen fluorine
The method of hydrochlorate is：Vacuum distillation is cooled to room temperature after terminating, and glycol dimethyl ether stirring and dissolving is added in reaction bulb, slowly
Excessive water is added dropwise, separates out dark thick material gradually, stands more than 30min, carries out filtering drying, obtains dark thick and consolidate
Body.
Embodiment
Embodiment 1
A kind of organic silicon-fluorine surface conditioning agent, it is using hexafluoropropylene trimer as modifying agent, using glycol dimethyl ether to be molten
Agent, using triethylamine as catalyst, pass through-the NH on aminopropyl triethoxysilane2The double bond of group and hexafluoropropylene trimer
Nucleophilic substitution occurs for fluorine atom, synthesizes the fluosilicic oxyalkane compound as shown in structural formula (VI).
(Ⅵ)：
Specific reactions steps are as follows：
Glycol dimethyl ether 90ml, triethylamine 6.9g, hexafluoropropylene trimer 30.6g are added into reaction bulb, stirring is equal
It is even, 30 DEG C of dropwise addition aminopropyl triethoxysilane 17g are warming up to, it is 50min to control time for adding, is added dropwise, is warming up to 60
DEG C reaction 3h；Reaction terminates, and 2h is evaporated under reduced pressure under the conditions of 0.1Mpa, 90 DEG C, removes solvent glycol dimethyl ether, the second of catalyst three
Amine and unreacted hexafluoropropylene trimer, obtain kermesinus thick substances；Running water 30g is added in reaction bulb, heating is stirred
Backflow 60min is mixed, is cooled to room temperature, is filtered, drying obtains target product, and then plus glycol dimethyl ether 30g, backflow are further
Purification, filtering drying obtain khaki powder shape solid.
Embodiment 2
A kind of organic silicon-fluorine surface conditioning agent, it is using hexafluoropropylene trimer as modifying agent, using glycol dimethyl ether to be molten
Agent, using triethylamine as catalyst, pass through-the NH of aminoethylaminopropyl methyl dimethoxysilane2Group and hexafluoropropene trimerization
Nucleophilic substitution occurs for the double bond fluorine atom of body, synthesizes the fluosilicic oxyalkane compound as shown in structural formula (VII).
(Ⅶ)：
Specific reactions steps are as follows：
Glycol dimethyl ether 100ml, triethylamine 6.9g, hexafluoropropylene trimer 30.6g are sequentially added into reaction bulb, is stirred
Mix uniformly, aminoethylaminopropyl methyl dimethoxysilane 14g is added dropwise after being warming up to 30 DEG C, it is 50min to control time for adding, drop
Add it is complete, be warming up to 50 DEG C reaction 3h；Reaction terminates, and vacuum distillation 2h is carried out under the conditions of 0.1Mpa, 90 DEG C, removes solvent two
Diethylene glycol dimethyl ether, catalyst of triethylamine and unreacted hexafluoropropylene trimer, obtain black liquor；Vacuum distillation cools down after terminating
To room temperature, glycol dimethyl ether 30ml stirring and dissolvings are added in reaction bulb, excessive water 20g is slowly added dropwise, separates out gradually black
Color thick substances, more than 30min is stood, carry out filtering drying, obtain dark thick solid.
Embodiment 3：
A kind of organic silicon-fluorine surface conditioning agent, it is using hexafluoropropylene trimer as modifying agent, using glycol dimethyl ether to be molten
Agent, using triethylamine as catalyst, be by general structure (III)Side chain
- NH on amido silicon oil2Nucleophilic substitution occurs for the double bond fluorine atom of group and hexafluoropropylene trimer, synthesizes structure such as and leads to
Fluorosiloxane copolymer shown in formula (VIII).
(Ⅷ)：
Specific reactions steps are as follows：
Glycol dimethyl ether 70ml, triethylamine 1.7g, the side-chain amino group as shown in formula (III) are added into reaction bulb successively
Silicone oil 40g, lead to nitrogen protection stirring, hexafluoropropylene trimer 7.4g is added dropwise at room temperature, it is 30min to control time for adding, is added dropwise
After add 30ml glycol dimethyl ethers and maintain room temperature 30min, then heat to 50 DEG C, react 3h；Reaction terminates,
0.1MPa, 2h is evaporated under reduced pressure under the conditions of 70 DEG C, removes low-boiling point material, obtain yellow transparent liquid.
Embodiment 4：
A kind of organic silicon-fluorine surface conditioning agent, it is using hexafluoropropylene trimer as modifying agent, with second
Glycol dimethyl ether is solvent, using triethylamine as catalyst, is by general structure (IV)Block gather
Nucleophilic substitution, synthesis such as structure occur for the double bond fluorine atom of-NH groups and hexafluoropropylene trimer on ether amido silicon oil
Fluorosiloxane copolymer shown in formula (Ⅸ).
(Ⅸ)：
Specific reactions steps are as follows：
Glycol dimethyl ether 70ml, triethylamine 1.7g, the block polyether as shown in formula (IV) are added into reaction bulb successively
Amido silicon oil 40g, lead to nitrogen protection stirring, hexafluoropropylene trimer 7.4g is added dropwise at room temperature, it is 30min to control time for adding,
30ml glycol dimethyl ethers are added after being added dropwise and maintain room temperature 30min, 50 DEG C is then heated to, reacts 3h；Reaction terminates,
0.1MPa, 2h is evaporated under reduced pressure under the conditions of 70 DEG C, removes low-boiling point material, obtain yellow transparent liquid.
Embodiment 5：
A kind of organic silicon-fluorine surface conditioning agent, it is using hexafluoropropylene trimer as modifying agent, using glycol dimethyl ether to be molten
Agent, using triethylamine as catalyst, be by general structure (V)'s
Ring-opening reaction, synthesis such as structure occur for the double bond fluorine atom of epoxide group and hexafluoropropylene trimer on epoxy based polysiloxane
Fluorosiloxane copolymer shown in formula (Ⅹ).
(Ⅹ)：
Specific reactions steps are as follows：
Glycol dimethyl ether 70ml, triethylamine 1.7g, the epoxy radicals silicon as shown in formula (V) are added into reaction bulb successively
Oily 40g, lead to nitrogen protection stirring, hexafluoropropylene trimer 7.4g is added dropwise at room temperature, it is 30min to control time for adding, is dripped
30ml glycol dimethyl ethers are added after finishing and maintain room temperature 30min, 80 DEG C is then heated to, reacts 3h；Reaction terminates,
0.1MPa, 2h is evaporated under reduced pressure under the conditions of 70 DEG C, removes low-boiling point material, use ethyl acetate:Methanol=10:1 is used as eluent, obtains
To brownish black thick liquid, finally decolourized, obtain the red thick liquid of grape.
Claims (9)
- A kind of 1. organic fluorinated silicone surface conditioning agent, it is characterised in that：The organic fluorinated silicone surface conditioning agent is:It is even with amino silane Reactant based on connection agent, amino silicones or epoxy based polysiloxane, using hexafluoropropylene trimer as modifying agent, with second two Diethylene glycol dimethyl ether is solvent, using triethylamine as catalyst, by reacting the fluosilicic oxyalkane compound of synthesis or being introduced on side chain complete The fluorosiloxane copolymer of fluoroalkyl.
- A kind of 2. organic fluorinated silicone surface conditioning agent according to claim 1, it is characterised in that：The hexafluoropropylene trimer Structural formula be：
- A kind of 3. organic fluorinated silicone surface conditioning agent according to claim 1, it is characterised in that：The amino silicones are Side-chain amino group silicone oil or block polyether amino silicone oil.
- A kind of 4. organic fluorinated silicone surface conditioning agent according to claim 1, it is characterised in that：The amino silicane coupling agent Structural formula be NH2CH2CH2CH2Si(OC2H5)3Or NH2CH2CH2NHCH2CH2CH2SiCH3(OCH3)2。
- A kind of 5. organic fluorinated silicone surface conditioning agent according to claim 3, it is characterised in that：The side-chain amino group silicone oil General structure is：In formula：X=NHC2H4NH2、NHC3H6N(CH3)2、N(C2H4NH2)2R=OH or CH3。
- A kind of 6. organic fluorinated silicone surface conditioning agent according to claim 5, it is characterised in that：The side-chain amino group silicone oil General structure is：
- A kind of 7. organic fluorinated silicone surface conditioning agent according to claim 3, it is characterised in that：The block polyether amino silicone Oil general structure be：Wherein：X=1-10；Y=1-10；Z=1-10.
- A kind of 8. organic fluorinated silicone surface conditioning agent according to claim 1, it is characterised in that：The epoxy based polysiloxane General structure be：
- A kind of 9. preparation method of organic silicon-fluorine surface conditioning agent, it is characterised in that：Including fluosilicic oxyalkane compound and fluorine silica The preparation method of alkane polymer, the preparation method of the fluosilicic oxyalkane compound comprise the following steps：Add successively into reaction bulb Enter glycol dimethyl ether, triethylamine, hexafluoropropylene trimer, stir, amino silane coupling is added dropwise after being warming up to 40-50 DEG C Agent, it is 30-50min to control time for adding, after being added dropwise under the conditions of 40-60 DEG C, reacts 3h；Reaction terminates, in 0.1Mpa, It is evaporated under reduced pressure under the conditions of 90 DEG C and removes solvent glycol dimethyl ether, catalyst of triethylamine and unreacted hexafluoropropylene trimer；It is logical Cross backflow or solution modeling method removes unreacted amino silicane coupling agent and accessory substance triethylamine hydrofluoride, to crude product Purified；The preparation method of the fluorosiloxane copolymer comprises the following steps：Sequentially added into reaction bulb glycol dimethyl ether, Triethylamine, amino silicones or epoxy based polysiloxane, lead to nitrogen protection stirring, hexafluoropropylene trimer be added dropwise at room temperature, It is 30-50min to control time for adding, and glycol dimethyl ether is added after being added dropwise and maintains room temperature 30min, then heats to 40- 60 DEG C, react 3h；Reaction terminates, and is evaporated under reduced pressure under the conditions of 0.1MPa, 70 DEG C and removes low-boiling point material.
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| CN106750320A (en) * | 2016-12-07 | 2017-05-31 | 衢州学院 | A kind of preparation method of perfluoroalkyl modified amido silicon oil |
| CN106832294B (en) * | 2017-01-21 | 2019-10-29 | 苏州逸微光电科技有限公司 | A kind of novel silicon-fluorine polymer object and surface treating agent |
| CN108299916A (en) * | 2017-09-18 | 2018-07-20 | 浙江汉邦化工有限公司 | The heat conduction anti-corrosion material additive and preparation method and application of a kind of graphene-containing and fluorosilicone compound |
| KR102570512B1 (en) * | 2017-11-07 | 2023-08-25 | 스미또모 가가꾸 가부시키가이샤 | laminate |
| CN109851738B (en) * | 2018-12-04 | 2021-03-26 | 广东坚派新材料有限公司 | Preparation method of fluorine-silicon modified carbamido compound |
| CN109796631B (en) * | 2018-12-26 | 2020-11-20 | 万华化学集团股份有限公司 | Modified inorganic nano particle, composite aqueous polyurethane resin and application thereof |
| CN115068696B (en) * | 2022-08-23 | 2022-10-21 | 山东百多安医疗器械股份有限公司 | Medical sputum suction tube with super-hydrophobic self-cleaning function and preparation method thereof |
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Address after: Jiaxing City, Zhejiang province 314500 Tongxiang City Fengming street strong industry road Patentee after: Zhejiang Hanbang new materials Co., Ltd Address before: Jiaxing City, Zhejiang province 314500 Tongxiang City Fengming street strong industry road Patentee before: Zhejiang Happy Chemical Co., Ltd. |